MatWerk Die inhaltliche Zielsetzung der Reihe ist es, das Fachgebiet „Materialwissenschaft und Werkstofft echnik“ (kurz MatWerk) durch hervorragende Forschungsergeb- nisse bestmöglich abzubilden. Dabei versteht sich die Materialwissenschaft und Werkstofft echnik als Schlüsseldisziplin, die eine Vielzahl von Lösungen für gesells- chaft lich relevante Herausforderungen bereitstellt, namentlich in den großen Zukunft sfeldern Energie, Klima- und Umweltschutz, Ressourcenschonung, Mobil- ität, Gesundheit, Sicherheit oder Kommunikation. Die aus der Materialwissenschaft gewonnenen Erkenntnisse ermöglichen die Her- stellung technischer Werkstoff e mit neuen oder verbesserten Eigenschaft en. Die Eigenschaft en eines Bauteils sind von der Werkstoff auswahl, von der konstruk- tiven Gestaltung des Bauteils, dem Herstellungsprozess und den betrieblichen Beanspruchungen im Einsatz abhängig. Dies schließt den gesamten Lebenszyklus von Bauteilen bis zum Recycling oder zur stoffl ichen Weiterverwertung ein. Auch die Entwicklung völlig neuer Herstellungsverfahren zählt dazu. Ohne diese stetigen Forschungsergebnisse wäre ein kontinuierlicher Fortschritt zum Beispiel im Maschinenbau, im Automobilbau, in der Luft fahrtindustrie, in der chemischen Industrie, in Medizintechnik, in der Energietechnik, im Umweltschutz usw. nicht denkbar. Daher werden in der Reihe nur ausgewählte Dissertationen, Habilitationen und Sammelbände veröff entlicht. Ein Beirat aus namhaft en Wis- senschaft lern und Praktikern steht für die geprüft e Qualität der Ergebnisse. Die Reihe steht sowohl Nachwuchswissenschaft lern als auch etablierten Ingenieurwis- senschaft lern off en. Christian Rockenhäuser Electron Microscopical Investigation of Interdiff usion and Phase Formation at Gd O |CeO and - 2 3 2 Sm O |CeO Interfaces - 2 3 2 With a Foreword by Prof. Dr. Dagmar Gerthsen 123 Christian Rockenhäuser Karlsruhe, Germany Dissertation, Karlsruhe Institute of Technology (KIT), 2014 MatWerk ISBN 978-3-658-08792-0 ISBN 978-3-658-08793-7 (eBook) DOI 10.1007/978-3-658-08793-7 Library of Congress Control Number: 2015933629 Springer © Springer Fachmedien Wiesbaden 2015 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, speci(cid:191) cally the rights of translation, reprinting, reuse of illus- trations, recitation, broadcasting, reproduction on micro(cid:191) lms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a speci(cid:191) c statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. Printed on acid-free paper Springer is a brand of Springer Fachmedien Wiesbaden Springer Fachmedien Wiesbaden is part of Springer Science+Business Media (www.springer.com) Electron Microscopical Investigation of Interdiffusion and Phase Formation at Gd O /CeO - and Sm O /CeO - 2 3 2 2 3 2 Interfaces Zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften von der Fakulta¨t fu¨r Physik des Karlsruher Instituts fu¨r Technologie (KIT) genehmigte Dissertation von Dipl.-Phys. Christian Rockenh¨auser aus Neuenbu¨rg Tag der mu¨ndlichen Pru¨fung: 27.06.2014 Referentin: Prof. Dr. D. Gerthsen Korreferent: Prof. Dr. M. J. Hoffmann angefertigt am Laboratorium fu¨r Elektronenmikroskopie Karlsruher Institut fu¨r Technologie (KIT) Partsandexcerpsofthisthesishavealreadybeenpublishedasjournalarticles. Figures are reprinted with permission: (cid:2)c 2013 Elsevier Reprinted (adapted) from the Journal of the European Ceramic Society 34 by C. Rockenha¨user, B. Butz, N. Schichtel, J. Janek, R. Oberacker, M. J. Hoff- mann, and D. Gerthsen, ”Microstructure evolution and cation interdiffusion in thinGd O filmsonCeO substrates”,Pages1235-1242,(cid:2)c 2013,withpermis- 2 3 2 sion from Elsevier. (cid:2)c 2014 American Ceramic Society Reprinted (adapted) from the Journal of the American Ceramic Society 97 by C. Rockenh¨auser, B. Butz, H. St¨ormer, and D. Gerthsen, ”Microstructure evo- lutionandcationinterdiffusioninthinSm O filmsonCeO substrates”,Pages 2 3 2 3276-3285, (cid:2)c 2014, with permission from Wiley-Blackwell (cid:2)c 2010 Christian Rockenh¨auser Partsofgraphsfrommydiplomathesis”Sm O -CeO interdiffusionstudiesby 2 3 2 transmission electron microscopy” are reprinted in adapted form. FFoorreewwoorrdd MMaatteerriiaallss wwiitthh hhigh igh oxygen-ion axygen-ion aanndd ne elgbigillgenigible eelleecetrtorno n ecoonndduuccttiviivtiy ty aarree neneeedded ed rrooff ffuuttuurer e ycneiciffe-hgihhigh-effieiency diloSSolid OOxixdie de FFuel uel slleCCells ((SSOOFFCCss)).. 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MMany any pproblems roblems ccould ould bbe e solved solved iin n so-callsed o-caJIed iintermedinate-temperature tennediate-temperature SSOOFCsF C. whweherree tthhee ooppeerraatitoino n tteemmppeerratautruerse s aarree derewollowered ttoo 0 00055 ttoo 770000°°CC.. UUp p ttoo ,w ,owonn YY2023-d0op,ed -doped ZZrr002 2 s isi tthhee ssttaattee--ooff--tthhee--aartr t SSOOFFC C eelleectcrtorloytley te mmaatteerriaila l bbuutt tthhee ooxxyyggeenn--iioonn ccoonndduuccttiivviittyy iinn tthhiiss mmaatteerriiaall bbeeccoommeess ttooDo llooww wwiitthh ddeeccrreeaassiinngg tteemmppeerraattuurree.. PoPossssibileb le aalltteerrnnataitviev e mmaatteerriiaall ssyysstteemmss aarree CCee002-based 2 -based eelelcetcrotlryotelsy.t es. EEsspepceicalilayl ly CCee020, 2 , ddooppeed d wwiitthh GGdd,03 2 0, oorr SSmm,O, 2 0 3 seseem em ttoo bbee prporommisiings, ing, bbeecaeuasue se tthheeyy aarre e cchhaararcateetreirzeidz ed bby y a a hihgighheerr axoxygeyn-ion gen-ion ccoonndduuccttiivviittyy ecoommppaarreedd ttoo Y Y -3022°, ddooppede d ZZrr00 22 . . TThhee axoxygeyn-ion gen-ion ccoonndduucettiivviittyy ooff tthheesse e mmaatteerirailasl s hhaass aallrreaedayd y been been tthoroughly horoughly sstudied, tudied, bhut ut oother ther bbasic asic mmaterial aterial pproperties roperties hhave ave yyet et nnot ot bbeen een niin vveessttiiggaatteedd r rooff tthheesse e rraarree--eeaartrht h oxidoxiede syssystteemmss.. TThhee PPhhDD tthheessiiss ooff DDr. r. CChhrriisstitaina n RoRckeonhiicusekr enhäuser sesuc soesufeof oonn two two aassppeeccttss.. FFiirrsstt,, pphhaases e ffoorrmamtaitoin on sawwas ssttuuddiieed d iinn tthhee 2/x_20x 2_/x'-e20CX._',eIC.<dGG aanndd 2/x-20x_'eC.mSSm.Ce"X02.x/2 ssyystsetmesm s aatt tteemmppeerratautruerse s wboelleobw 00002211 °°C. c. BBaassede d oonn tthheessee ssttuuddiieess cocncolunsciolnsu sions erewerew ddrraawwn n wwiitthh rreesspepcete t ttoo tthhee ssuuiittaabibliiltiyt y ooff tthheesse e mmaatteerriiaallss aass SSOOFCF C coempoom po nneennttss.. SSeeccoonndd,, ccaattiioonn iinntteerrddiiffffuussiioonn ccooeeffffiicciieennttss wweerree ddeetteerrmmiinneedd aanndd aaccttiivvaattiioonn eenntthahlaplipeis es ro frof CCee/jGGdd-- aanndd CCee/jSSmm-c-aetaitoino n initnteerrddififufsifoun sion erew erew derdiveed.r ived. TThhiin-nfi-lm illm cocupoluesp les erewerew ususeedd tthhrroouugghhoouutt tthhee ,krowwork, which which erew erew iinnvvesetsitgiatgeadt ed bbyy aannaallyyt t iiccaal l 'Transmission Transmission EElleecetrtorno n Mic ypocsorciMroseopy ((TTEEMM)).. 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AAn n iinnttrroodducuteitoino n ooff diffedreint fferent TTEEMM tetecchhnniqiuqesu es aanndd aannaallyytitciacla l mmeetthhooddss siis ,ne v,nievgig whwhich ich erew erew aapppplliieedd iinn tthhiiss .kr .okrwow PPaarrttiiceuullaar r eemmphpahsaiss is s saaww llaaidi d oon n tthe he qquantification uantification oof f ccomposition omposition seliforpprofiles bby y EEnergy-Dispersive nergy-Dispersive XX-ray -ray cepSSpec ttrroossceopoy py )(SXEDDEX(S) aanndd EElleeccttrroonn EEnneergryg y ss ossLoL SSppecetcrtosrcoospey opy (E(ELESE) LS) ppeerfrofromredm ed wwiitthh hhiigghh ssppaattiiaall rreessoolluuttiioonn iinn aa ttrraannssmmiissssiioonn eelleeccttrroonn mmiiccrroossccooppee.. TThhee wwoorrkk VVIIIIII FFoorreewwoarrdd aaddddrreesssseess aaddvvaanncceedd ssttuuddeennttss aanndd eexxppeerriieenncceedd sscciieennttiissttss aanndd eennggiinneeeerrss iinn bbaassiicc aanndd aapppplliieedd mmaatteerriiaallss sscciieennccee.. PPrrooff.. DDrr.. DDaaggmmaarr GGeerrtthhsseenn LLaabboorraattoorryy rrooff EElleeccttrroonn yyppooccssoorrcciiMM KKaarrllssrruuhhee IInnssttiittuuttee ooff yyggoolloonnhhcceeTT ((KKIITT)) Acknowledgement I want to thank Everyone, who contributed to the successful completion of my dissertation. FirstandforemostIexpressmygratitudetoProf. Gerthsenfortheexcellent supervision and that she made this work possible at the LEM. Her patient revision of my manuscripts helped me a great deal – formulating scientifically correctandprecisedoesnotonlyrequirepractice,butalsoinstructionon”how on does it”. I also want to thank to be given the possibility to participate in conferences. I thank Prof. Hoffmann for the giving the second assessment and the friendly help and support at the IAM-KM with the fabrication of the CeO 2 substrates and targets for the PLD. IalsothankNicoleSchichtelandProf. JanekatthePhysikalisch-Chemischen Institut for the thin film deposition utilizing PLD. I am grateful to Benjamin Butz for giving the initial impulse to this study. Additionally I was introduced into operating electron microscopes by him and thank him for many productive hours at the microscope. Many thanks go to Heike Sto¨rmer for the correction of several manuscripts and parts of the thesis. And also the discussions about phase diagrams helped me very much. I also want to give a big thank you to Miss Sauter, who always had some encouragin words for me in every situation. I also want to express kind regards to my colleagues at the LEM. The discussion of various physical, non-physical and meta-physical topics in the ”Kaffeeraum”(coffee room) were very enriching as well as the exquisite pastrys of the ”Backstubenba¨cker”. The LEM-Lauffreunde are also very important, since they see to it that one does not only sit at the desk. Manythankstomymomanddad,Florian,Lisa-Marie,Annerose,Wolfgang, and Heike for motivation and support when I needed it. Stefan,withoutyouIwouldnotsucceeded! Thankyou,thatyouwerethere for me! Dr. Christian Rockenha¨user